KR101710170B1 - Recycling process of waste stripper for photoresist - Google Patents
Recycling process of waste stripper for photoresist Download PDFInfo
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- KR101710170B1 KR101710170B1 KR1020150097659A KR20150097659A KR101710170B1 KR 101710170 B1 KR101710170 B1 KR 101710170B1 KR 1020150097659 A KR1020150097659 A KR 1020150097659A KR 20150097659 A KR20150097659 A KR 20150097659A KR 101710170 B1 KR101710170 B1 KR 101710170B1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
Abstract
The present invention relates to a regenerating solution containing 40 wt% to 75 wt% of at least one amine compound, 20 wt% to 55 wt% of an alkylene glycol compound and 1 wt% to 10 wt% of an additive, And a method of regenerating a stripper waste solution for a photoresist.
Description
The present invention relates to a method for regenerating a stripper waste solution for a photoresist. More specifically, it is possible to reduce the analysis time of the raw material and the dilution time of the additive, thereby improving the production speed and reducing the cost. The raw material and the additive are added in a predetermined amount to prepare a photoresist stripper And a method for regenerating a stripper waste solution for a photoresist capable of reducing a content error between strippers.
The microcircuit process of a liquid crystal display device or the process of manufacturing a semiconductor integrated circuit may be a process of forming a conductive metal film or silicon oxide film such as aluminum, aluminum alloy, copper alloy, molybdenum or molybdenum alloy on the substrate or an insulating film such as a silicon nitride film or a fork acrylic insulating film Forming a photoresist pattern uniformly on the lower film, selectively exposing and developing the photoresist to form a photoresist pattern, and patterning the lower film using the photoresist pattern as a mask. After the patterning process, the photoresist remaining on the lower film is removed. For this purpose, a stripper composition for removing photoresist is used.
On the other hand, the stripper waste liquid generated during the manufacturing process of an electronic component such as a semiconductor wafer or a liquid crystal display glass substrate contains impurities such as moisture and heavy metals together with a photoresist resin in addition to a stripper solvent. Most of these stripper wastes are incinerated as process fuels or are only recycled at a low level, resulting in secondary pollution sources, inefficient energy consumption and environmental pollution and weakening competitiveness of the IT industry.
Furthermore, in the case of LCD production in which stripper waste liquid is most discharged due to the rapid development of IT technology, a 7th generation production line capable of manufacturing not only commercialized 40 to 47 inch LCD panels but also 82 inch size products is in operation, As the size of the LCD substrate is rapidly increasing and the types of substrates are diversified as the 9th generation production line development plan is established, the volume of the stripper solvent is also increasing proportionally.
Considering this reality, recycling technology for stripper waste liquid which can produce a high-purity regenerated stripper solvent at a low cost beyond the simple regeneration level of the stripper waste liquid becomes more urgent.
Accordingly, a technique has been proposed in which a stripper waste solution is purified, each raw material is recovered, each raw material is analyzed, and an additive diluted in a solvent is added to regenerate the stripper. However, it takes much time and expense to dilute the additive into the solvent by recovering the respective raw materials, and the efficiency of the process is decreased. In addition, when the additive is diluted in the solvent, There is a limit in which the addition of the additive is difficult.
Therefore, it is required to develop a new stripper regeneration process which can reduce the time consumed for material analysis and solvent dilution, and can add a predetermined amount of additives.
The present invention can reduce the analysis time of the raw material and the dilution time of the additive, thereby improving the production speed and reducing the cost. In addition, the raw material and the additive are added in a fixed amount, and the regenerated stripper Which is capable of producing a photoresist stripper waste solution.
In the present specification, a regeneration solution containing 40 wt% to 75 wt% of at least one amine compound, 20 wt% to 55 wt% of an alkylene glycol compound and 1 wt% to 10 wt% of an additive, And a method of regenerating a stripper waste solution for a photoresist.
Hereinafter, a method for regenerating a photoresist stripper waste solution according to a specific embodiment of the present invention will be described in detail.
According to one embodiment of the invention, a regeneration solution comprising 40 wt% to 75 wt% of at least one amine compound, 20 wt% to 55 wt% of an alkylene glycol compound, and 1 wt% to 10 wt% And a step of bringing the stripper solution into contact with a purification liquid of the waste solution.
The inventors of the present invention have found that the use of the regenerating solution containing a certain amount of the material necessary for producing the photoresist stripper makes it possible to reduce the analysis time for the raw material and the dilution of the additive In addition to reducing production time and cost while improving production speed, it is also possible to produce regenerated stripper products with the same quality as new photoresist strippers before recycling by injecting raw materials and additives in quantitative amounts. And completed the invention.
Specifically, the regeneration method of the photoresist stripper waste solution comprises a regenerating solution containing 40 wt% to 75 wt% of at least one amine compound, 20 wt% to 55 wt% of an alkylene glycol compound, and 1 wt% to 10 wt% With a refining liquid of a photoresist stripper waste liquid. The regenerating solution is diluted in the alkylene glycol compound solvent in the state that the additives and the like which are not contained in the purified solution of the photoresist stripper waste solution are analyzed and filtered so that the analysis time and the filtering time can be shortened Thereby reducing costs. In addition, the amount of the additive to be added in a small amount can be accurately supplied, and a regenerated product of the same quality as that of the new photoresist stripper before the regenerating process can be produced.
The regeneration solution may comprise at least one amine compound. The amine compound is a component exhibiting a peeling force, and may function to dissolve and remove the photoresist.
Examples of the amine compound include, but are not limited to, (2-aminoethoxy) -1-ethanol; AEE), aminoethyl ethanolamine (AEEA), monomethanolamine, monoethanolamine, N-methylethylamine (N-MEA), 1-aminoisopropanol Examples of the solvent include methyl dimethyl amine (MDEA), diethylene triamine (DETA), 2-methylaminoethanol (MMEA), 3-aminopropanol (AP), diethanolamine Chain amines such as diethanolamine (DEA), diethylaminoethanol (DEEA), triethanolamine (TEA) and triethylene tetraamine (TETA), or imidazolyl- Cyclic amine compounds such as 4-ethanol (IME), amino ethyl piperazine (AEP), and hydroxyl ethylpiperazine (HEP) can be used.
The regeneration solution may contain 40 wt% to 75 wt% of the at least one amine compound. If the amount of the at least one amine compound is less than 40% by weight based on the total regeneration solution, the content of the amine compound in the finally regenerated photoresist stripper is decreased, and the stripping force of the regenerated photoresist stripper is decreased . If the content of the amine compound exceeds 75 wt% with respect to the entire regenerating solution, the content of the amine compound in the regenerated photoresist stripper is excessively increased, so that corrosion of the lower film, for example, And it may be necessary to use a large amount of corrosion inhibitor to suppress it. In this case, a significant amount of the corrosion inhibitor is adsorbed and remains on the surface of the lower film due to a large amount of the corrosion inhibitor, so that the electrical characteristics of the copper-containing lower film and the like may be lowered.
The alkylene glycol compound contained in the regeneration solution may be a material well known in the art, and the kind thereof is not particularly limited. For example, the alkylene glycol compound may be selected from the group consisting of bis (2-hydroxyethyl) ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl But are not limited to, ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tri The Propylene glycol monopropyl ether, and the like, or tri propylene glycol monobutyl ether, may be used in combination of two or more selected among them. (2-hydroxyethyl) ether (HEE) may be used as the alkylene glycol or alkylene glycol monoalkyl ether in consideration of the excellent wettability of the stripper composition in one embodiment, and hence the improved peeling force and rinse force. Or diethylene glycol monobutyl ether (BDG) may be suitably used.
The alkylene glycol compound is present in an amount ranging from 20 wt% to 55 wt% with respect to the entire regeneration solution, so that the peeling force of the finally regenerated photoresist stripper can be secured and the peeling force and rinsing force Can be maintained over a long period of time.
In addition, the regeneration solution may further include an additive. As described above, since the regenerant solution is diluted with the alkylene glycol compound solvent in a state in which the trace amount of the additive is analyzed and filtered, the analysis time and the filtering time can be shortened and the cost can be reduced accordingly. In addition, the amount of the additive to be added in a small amount can be accurately supplied, and a regenerated product of the same quality as that of the new photoresist stripper before the regenerating process can be produced.
In addition, the additive may be included in the regeneration solution in an amount of 1 wt% to 10 wt%, or 2 wt% to 9 wt%, or 4 wt% to 8 wt%.
The additive may include a corrosion inhibitor or a silicone-based nonionic surfactant. The weight ratio of the anti-corrosion agent and the silicone-based nonionic surfactant may be from 5: 1 to 15: 1, or from 7: 1 to 12: 1, or from 8: 1 to 10: 1, or from 8.5: 1 to 9.5: 1.
Examples of the corrosion inhibitor include a benzimidazole-based compound, a triazole-based compound, and a tetrazole-based compound.
Examples of the benzimidazole compound include, but are not limited to, benzimidazole, 2-hydroxybenzimidazole, 2-methylbenzimidazole, 2- (hydroxymethyl) benzimidazole, 2- Capto benzimidazole, and the like, and examples of the tetrazole-based compound include 5-aminotetrazole or a hydrate thereof.
In addition, the triazole-based compound may include a compound represented by the following formula (1) or (2).
[Chemical Formula 1]
Wherein R9 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R10 and R11 are the same or different and each is a hydroxyalkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 4,
(2)
Wherein R12 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
and b is an integer of 1 to 4.
More specifically, in the above formula (1), R9 is a methyl group, R10 and R11 are each a hydroxyethyl group, and a is 1, or a compound wherein R12 is a methyl group and b is 1 in the formula (2).
By using the above-mentioned corrosion inhibitor, it is possible to effectively maintain the peeling force and the like of the stripper composition while effectively suppressing the corrosion of the metal-containing lower film.
The corrosion inhibitor may be included in the regeneration solution in an amount of 1 wt% to 10 wt%, or 2 wt% to 9 wt%, or 4 wt% to 8 wt%. If the content of the corrosion inhibitor is less than 1% by weight with respect to the regeneration solution, the content of the corrosion inhibitor in the finally regenerated photoresist stripper is reduced, and it may be difficult to effectively suppress corrosion on the lower film. If the content of the corrosion inhibitor is more than 10% by weight with respect to the regeneration solution, as the content of the corrosion inhibitor in the finally regenerated photoresist stripper is excessively increased, a considerable amount of the corrosion inhibitor is adsorbed and remains on the lower film So that the electrical characteristics of the copper-containing lower film and the like can be lowered.
On the other hand, the silicone-based nonionic surfactant may include a polysiloxane-based polymer. More specifically, examples of the polysiloxane-based polymer include polyether-modified acrylic functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether- Roxy functional polydimethylcellulose, polyether-modified dimethylpolysiloxane, modified acrylic functional polydimethylsiloxane, or a mixture of two or more of these.
The silicone-based nonionic surfactant may be contained in an amount of 0.1 wt% to 0.9 wt%, or 0.2 wt% to 0.8 wt%, or 0.3 wt% to 0.7 wt% based on the regeneration solution. When the content of the silicone-based nonionic surfactant is less than 0.1% by weight based on the regeneration solution, the content of the silicone-based nonionic surfactant in the finally regenerated photoresist stripper decreases, and the peeling force and rinsing power The improvement effect may not be sufficiently obtained. When the content of the silicone-based nonionic surfactant is more than 0.9% by weight based on the regeneration solution, the content of the silicone-based nonionic surfactant in the finally regenerated photoresist stripper is excessively increased, Bubbles may be generated at high pressure during the process, resulting in unevenness in the lower film or malfunction of the equipment sensor.
On the other hand, the regeneration solution containing 40 wt% to 75 wt% of the at least one amine compound, 20 wt% to 55 wt% of the alkylene glycol compound and 1 wt% to 10 wt% of the additive is mixed with the refining liquid of the photoresist stripper waste solution In the contacting step, the weight ratio of the refining solution and regeneration solution of the photoresist stripper waste solution may be from 5: 1 to 20: 1, or from 7: 1 to 15: 1, or from 8: 1 to 12: 1. By adjusting the weight ratio of the refining solution and the regeneration solution of the photoresist stripper waste solution to the above range, the composition ratio of the finally produced regenerating stripper can be secured to almost the same level as that of the original product before regeneration. If the weight ratio of the refined solution of the photoresist stripper waste solution and the regenerating solution is less than 5: 1, the proportion of the refined solution of the photoresist stripper waste solution becomes smaller, The content of N-methylformamide contained in only the purified liquid of the stripper waste liquid may be excessively small. If the weight ratio of the refining solution and the regenerating solution of the photoresist stripper waste solution is more than 20: 1, the photoresist stripper waste solution is not included in the refining solution of the photoresist stripper waste solution, The content of other additives contained only in the solution may become too small.
The regeneration solution containing 40 wt% to 75 wt% of the at least one amine compound, 20 wt% to 55 wt% of the alkylene glycol compound, and 1 wt% to 10 wt% of the additive is contacted with the refining liquid of the photoresist stripper waste solution Step may further include contacting at least one selected from the group consisting of an aprotic organic solvent and a quantum organic solvent together with a refining solution and a regeneration solution of the photoresist stripper waste solution.
Specifically, 60 wt% to 95 wt% of the purified solution of the photoresist stripper waste solution; 1% to 10% by weight of the regeneration solution; And 1% by weight to 30% by weight of at least one compound selected from the group consisting of an aprotic organic solvent and a quantum organic solvent.
The amphipathic polar solvent can properly dissolve the amine compound, while allowing the regenerated stripper to appropriately impregnate on the lower film on which the photoresist pattern to be removed remains, so that excellent peeling force and rinsing force can be secured.
Examples of the aprotic organic solvent include, but are not limited to, N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylsulfoxide (DMSO) Dimethylformamide (DMF), N-methylformamide (NMF), N, N'-diethylcarboxamide (DCA), dimethylpropionamide (DMP) and the like can be used.
The protonic polar solvent allows the regenerated stripper to better impregnate on the lower film, thereby assisting in an excellent peeling force and effectively removing the stain on the lower film such as the copper containing film, thereby improving the rinse force.
The protonic polar solvent may include an alkylene glycol or an alkylene glycol monoalkyl ether. More specifically, the alkylene glycol or alkylene glycol monoalkyl ether is selected from bis (2-hydroxyethyl) ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropyl Glycol monoethyl ether, tripropylene glycol monopropyl ether, triethylene may include propylene glycol mono-butyl ether or combinations of two or more thereof.
The refining liquid of the photoresist stripper waste solution contains the aprotic organic solvent and the quantitative organic solvent at a weight ratio of 0.6: 1 to 1.8: 1, or 0.7: 1 to 1.7: 1, or 0.8: 1 to 1.65: 1 . The non-magnetic organic solvent and the quantum organic solvent contained in the purified solution of the photoresist stripper waste solution are selected from the group consisting of an aprotic organic solvent and a quantum organic solvent together with the purified solution and regeneration solution of the photoresist stripper waste solution The above-mentioned contents are included in the step of contacting one or more.
The purified liquid of the photoresist stripper waste solution may further contain 0.1% by weight to 10% by weight of an amine compound. As described above, the purified liquid of the stripper waste solution for photoresist contains an aprotic organic solvent and a quantitative organic solvent, and the aprotic organic solvent may cause an aging reaction with the amine. However, when a small amount of amine is added to the purified liquid .
The regeneration solution containing 40 wt% to 75 wt% of the at least one amine compound, 20 wt% to 55 wt% of the alkylene glycol compound, and 1 wt% to 10 wt% of the additive is contacted with the refining liquid of the photoresist stripper waste solution Prior to the step, the stripper waste solution for photoresist may be further purified. The step of purifying the photoresist stripper waste solution can effectively and economically remove solid matter, impurities and moisture from the photoresist stripper waste solution collected after the use of the photoresist stripper solution in the manufacturing process of semiconductor, display device, LED or solar cell The stripper of high purity can be recovered.
Specifically, the step of purifying the photoresist stripper waste liquid includes a step of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr, and distilling the photoresist stripper waste liquid . The step of purifying the photoresist stripper waste liquid comprises the steps of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr and distilling the photoresist stripper waste solution, The solid content is removed from the stripper waste solution, and at the same time, the photoresist having a boiling point of 235 DEG C or higher can be removed together. In the step of purifying the photoresist stripper waste liquid, a distillation tank or the like may be used in order to recover the purified liquid in accordance with the difference in boiling point, as described above. Although specific examples of the distillation column are not limited, for example, general single distillation, rechargeable or multi-stage distillation columns can be used. The distillation column refers to an experimental apparatus that uses a principle of fractional distillation, which is a method of separating a mixed liquid mixture by boiling point difference.
If the temperature of the distillation column is less than 100 ° C, the waste solution of the photoresist stripper can not be completely distilled, and thus the effective component is removed together with the solid component and the photoresist, thereby lowering the recovery rate of the waste solution. If the temperature of the distillation tower is higher than 200 ° C, there is a possibility that thermal decomposition and deformation of an effective component in the waste solution may occur, and some components of the photoresist and the solid component may not be removed, thereby causing problems in the purification process. In addition, when the pressure condition is less than 60 torr, it may be difficult to use in a commercial process due to a cost problem. If the pressure exceeds 140 torr, the stripper waste solution can not be completely distilled even if the temperature is raised sufficiently. It may be removed together with the resist so that the recovery rate of the waste solution may be lowered.
The lower part of the distillation column is maintained at a temperature of 100 ° C to 200 ° C and a temperature of 70 ° C to 200 ° C after the step of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr, distilling the upper portion of the distillation column at a temperature of 50 DEG C to 110 DEG C and a pressure of 10 torr to 50 torr at a pressure of from torr to 130 torr; And distilling the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 torr to 130 torr; As shown in FIG.
Specifically, the lower portion of the distillation column is distilled at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 torr to 50 torr Step, the low boiling point mixture can be removed from the stripper waste liquid from which the solids have been removed. The low boiling point mixture means an impurity having a boiling point lower than that of the stripper solvent contained in the photoresist stripper waste liquid. The lower part of the distillation tower specifically refers to the lowest point nearest to the ground in the distillation tower with respect to the ground, and can maintain a high temperature, so that a liquid vaporized at a high temperature can be obtained. On the other hand, the upper part of the distillation tower refers specifically to the uppermost point of the distillation tower, which is the farthest from the surface of the distillation tower with respect to the ground, and relatively low temperature can be maintained as compared with the lower part of the distillation tower, have.
The lower part of the distillation tower is distilled at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper part of the distillation tower at a temperature of 120 ° C to 180 ° C and a pressure of 70 torr to 130 torr The high boiling point mixture can be removed from the stripper waste solution from which the low boiling point mixture has been removed. The high boiling point mixture means an impurity having a boiling point higher than that of the stripper solvent contained in the photoresist stripper waste solution.
Meanwhile, after the entire distillation column is maintained at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr, the bottom of the distillation column is distilled at a temperature of 100 ° C to 200 ° C And distilling the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 torr to 130 torr at a pressure of 70 torr to 130 torr; And distilling the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 torr to 50 torr; As shown in FIG.
The lower part of the distillation column is distilled at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while the upper part of the distillation column is maintained at a temperature of 120 ° C to 180 ° C and a pressure of 70 torr to 130 torr , The high boiling point mixture can be removed from the stripper waste liquid from which the solid matter has been removed.
And distilling the upper part of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the lower part of the distillation tower at a temperature of 50 ° C to 110 ° C and a pressure of 10 torr to 50 torr The low boiling point mixture can be removed from the stripper waste solution from which the high boiling point mixture has been removed.
According to the present invention, it is possible to reduce the analysis time of the raw material and the dilution time of the additive, thereby improving the production speed and reducing the cost. In addition, the raw material and the additive are added in a predetermined amount, A method of regenerating a stripper waste solution for a photoresist capable of producing a regenerated product of the stripper can be provided.
The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
≪ Preparation Examples 1 to 20: Preparation of stripper refining liquid >
The solid content was removed from the stripper waste liquid generated by using the stripper fresh liquid having the composition shown in the following Table 1 in the manufacturing process of electronic parts under a pressure of 100 Torr at a temperature of 150 ° C using a multi-stage distillation column. Then, the lower portion of the multi-stage distillation column was maintained at a temperature of 150 ° C. and a pressure of 100 torr, and the upper portion of the multi-stage distillation column was maintained at a temperature of 100 ° C. and a pressure of 30 torr to remove the low boiling point mixture. The lower portion of the multi-stage distillation column was maintained at a temperature of 150 ° C. and a pressure of 100 torr, the temperature of the multi-stage distillation column was maintained at 130 ° C. and a pressure of 100 torr to remove the high boiling point mixture, .
< Manufacturing example 21: Preparation of regeneration solution >
A regeneration solution was prepared so as to have the composition shown in Table 3 below.
< Example 1 to 20: Playback Stripper Manufacturing>
The regeneration solution obtained in Preparation Example 21 and N-methylformamide and diethylene glycol monobutyl ether were put into a stirrer at the weight ratios shown in Table 4 below and stirred at room temperature for 45 minutes To obtain a regenerating stripper having the composition shown in Table 5 below.
(weight%)
(weight%)
(weight%)
(weight%)
(weight%)
(weight%)
IME: Imidazolyl-4-ethanol (IMD)
* AEE: (2-aminoethoxy) -1-ethanol
* NMF: N-methylformamide
* BDG: diethylene glycol monobutyl ether
* First corrosion inhibitor: [[(methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol
* Second corrosion inhibitor: benzimidazole
* Surfactants: polyether modified polydimethylsiloxane
As shown in Table 5, the regenerating strippers of Examples 1 to 20 contained 3.0% by weight of imidazolyl-4-ethanol; 1.0% by weight of (2-aminoethoxy) -1-ethanol; 54% to 56% by weight of N-methyl formamide; 39% to 42% by weight of diethylene glycol monobutyl ether; [[(Methyl-1H-benzotriazol-1-yl) methyl] imino] bis ethanol 0.3% by weight; 0.15 wt% benzimidazole; 0.0 > 0.05% < / RTI > by weight of polyether modified siloxane.
The photoresist stripper fresh solution before the regeneration treatment shown in Table 1 was prepared by adding 3.0% by weight of imidazolyl-4-ethanol; 1.0% by weight of (2-aminoethoxy) -1-ethanol; 54.5% by weight of N-methylformamide; 41% by weight of diethylene glycol monobutyl ether; [[(Methyl-1H-benzotriazol-1-yl) methyl] imino] bis ethanol 0.3% by weight; 0.15 wt% benzimidazole; Among the components contained in the regenerating strippers of Examples 1 to 20, it is preferable to use imidazolyl-4-ethanol, (2-aminoethoxy) -1-ethanol, [[ (Methyl-1H-benzotriazol-1-yl) methyl] imino] bisethanol, benzimidazole and polyether modified siloxane showed the same contents as the photoresist stripper fresh solution before the regenerating treatment have.
Also, in the case of N-methylformamide and diethylene glycol monobutyl ether among the components contained in the regeneration strippers of Examples 1 to 20, 54 wt% to 56 wt% of N-methylformamide; And 54% by weight of N-methylformamide and 41% by weight of diethylene glycol monobutyl ether contained in the photoresist stripper fresh solution shown in Table 1, containing 39% by weight to 42% by weight of diethylene glycol monobutyl ether Respectively.
As described above, even if the regeneration process of the regenerating strippers of Examples 1 to 20 is repeated, the raw materials and the additives can be supplied in a predetermined amount, and the quality can be maintained uniform. Even in the regenerated photoresist stripper, It can achieve the same level of quality as the new stripper. Particularly, a mixture of 0.3% by weight of an additive ([[(methyl- 1H-benzotriazol-1-yl) methyl] imino] bis ethanol added in a small amount, 0.15% by weight of benzimidazole, 0.05% by weight of polyether modified siloxane) , It can be confirmed that the photoresist stripper fresh solution before the regenerating process can be regenerated at a precise level enough to contain the same content without error.
Claims (16)
Contacting the regeneration solution containing 40 wt% to 75 wt% of at least one amine compound, 20 wt% to 55 wt% of an alkylene glycol compound, and 1 wt% to 10 wt% of an additive with a refining liquid of a photoresist stripper waste solution Lt; / RTI >
Wherein the step of purifying the photoresist stripper waste liquid comprises the steps of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr to distill the photoresist stripper waste liquid,
Wherein the weight ratio of the refining solution and the regeneration solution of the photoresist stripper waste solution is 5: 1 to 20: 1.
The regeneration solution containing 40 wt% to 75 wt% of the at least one amine compound, 20 wt% to 55 wt% of the alkylene glycol compound, and 1 wt% to 10 wt% of the additive is contacted with the refining liquid of the photoresist stripper waste solution In the step,
Further comprising the step of contacting at least one selected from the group consisting of an aprotic organic solvent and a quantitative organic solvent together with the purified solution and regeneration solution of the photoresist stripper waste solution.
The step of contacting at least one selected from the group consisting of an aprotic organic solvent and a quantum organic solvent together with a refining solution and a regeneration solution of the photoresist stripper waste solution,
60 wt% to 95 wt% of the purified liquid of the photoresist stripper waste solution;
1% to 10% by weight of the regeneration solution; And
And 1% by weight to 30% by weight of at least one compound selected from the group consisting of an aprotic organic solvent and a quantum organic solvent.
Wherein the refining solution of the photoresist stripper waste solution contains an aprotic organic solvent and a quantitative organic solvent at a weight ratio of 0.5: 1 to 2: 1.
Wherein the refining solution of the photoresist stripper waste solution further comprises an amine compound in an amount of 0.1 wt% to 10 wt%.
Wherein the additive comprises at least one selected from the group consisting of a corrosion inhibitor and a silicone-based nonionic surfactant.
Wherein the weight ratio of the corrosion inhibitor and the silicone-based nonionic surfactant is from 5: 1 to 15: 1.
Wherein the corrosion inhibitor comprises a benzimidazole-based compound, a triazole-based compound, and a tetrazole-based compound.
Wherein the triazole-based compound comprises a compound represented by the following formula (1) or (2):
[Chemical Formula 1]
Wherein R9 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R10 and R11 are the same or different and each is a hydroxyalkyl group having 1 to 4 carbon atoms,
a is an integer of 1 to 4,
(2)
Wherein R12 is hydrogen or an alkyl group having 1 to 4 carbon atoms,
and b is an integer of 1 to 4.
Wherein the silicone-based nonionic surfactant comprises a polysiloxane-based polymer.
Wherein the polysiloxane polymer is selected from the group consisting of polyether modified acrylic functional polydimethylsiloxane, polyether modified siloxane, polyether modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl modified polymethylalkylsiloxane, polyether modified hydroxy functional polydimethylsiloxane , A polyether-modified dimethylpolysiloxane, and a modified acrylic functional polydimethylsiloxane. ≪ Desc / Clms Page number 19 >
After the step of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr and distilling the photoresist stripper waste solution,
Distilling the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 torr to 50 torr; And
Distilling the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 torr to 130 torr; Wherein the photoresist stripper waste solution is a photoresist stripper waste solution.
After the step of maintaining the entire distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 60 torr to 140 torr and distilling the photoresist stripper waste solution,
Distilling the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 120 ° C to 180 ° C and a pressure of 70 torr to 130 torr; And
Distilling the lower portion of the distillation column at a temperature of 100 ° C to 200 ° C and a pressure of 70 torr to 130 torr while maintaining the upper portion of the distillation column at a temperature of 50 ° C to 110 ° C and a pressure of 10 torr to 50 torr; Wherein the photoresist stripper waste solution is a photoresist stripper waste solution.
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| CN201580012366.3A CN106062638B (en) | 2014-08-20 | 2015-07-10 | Method for recovering waste photoresist stripper |
| JP2016550833A JP6336608B2 (en) | 2014-08-20 | 2015-07-10 | Recycling method for stripper waste liquid for photoresist |
| PCT/KR2015/007199 WO2016027986A1 (en) | 2014-08-20 | 2015-07-10 | Regeneration method for stripping wastewater for photoresist |
| TW104124620A TWI569112B (en) | 2014-08-20 | 2015-07-30 | Process for recycling waste photoresist stripper |
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| KR102209389B1 (en) * | 2016-09-26 | 2021-01-28 | 주식회사 엘지화학 | Refining process of waste stripper for removing photoresist |
| CN108926860B (en) * | 2018-07-20 | 2021-12-21 | 上海化工研究院有限公司 | Waste stripping liquid regeneration device and application thereof |
| CN110818539B (en) * | 2019-11-05 | 2022-08-19 | 安庆市鑫祥瑞环保科技有限公司 | Method for purifying diethylene glycol monobutyl ether reagent from waste stripping liquid |
| CN110923025B (en) * | 2019-12-09 | 2022-01-28 | 福建中融科技有限公司 | Fuel oil produced by using distillation residues of waste stripping liquid and production method thereof |
| CN111427243A (en) * | 2020-02-12 | 2020-07-17 | 惠州达诚微电子材料有限公司 | Regeneration method of photoresist stripping liquid |
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| JP4144825B2 (en) * | 1999-04-21 | 2008-09-03 | 東京応化工業株式会社 | Recycling method of used resist stripping solution |
| KR20040009100A (en) * | 2002-07-22 | 2004-01-31 | 삼성전자주식회사 | Photoresist stripper recycling method |
| JP3953476B2 (en) * | 2003-06-26 | 2007-08-08 | ドングウー ファイン−ケム カンパニー、 リミテッド | Photoresist stripping liquid composition and photoresist stripping method using the same |
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| JP4773562B2 (en) * | 2006-05-26 | 2011-09-14 | エルジー・ケム・リミテッド | Stripper composition for photoresist |
| JP4476356B2 (en) * | 2007-09-05 | 2010-06-09 | コレックス コーポレーション | Photoresist stripper waste liquid recycling method and recycling apparatus, and method for improving its recovery rate |
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